EP1577708A2 - Photosensitive resin composition and use of the same - Google Patents
Photosensitive resin composition and use of the same Download PDFInfo
- Publication number
- EP1577708A2 EP1577708A2 EP05005613A EP05005613A EP1577708A2 EP 1577708 A2 EP1577708 A2 EP 1577708A2 EP 05005613 A EP05005613 A EP 05005613A EP 05005613 A EP05005613 A EP 05005613A EP 1577708 A2 EP1577708 A2 EP 1577708A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- film
- resin composition
- photosensitive resin
- carbon atoms
- pattern
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
Definitions
- the present invention relates to a photosensitive resin composition capable of forming, with high resolution, a pattern comprising a polyimide film having a thickness of 20 ⁇ m or larger.
- the invention further relates to a use of the composition, in particular, a method of forming a pattern comprising the polyimide film.
- Thin inorganic films formed by CVD have usually been used as interlayer insulating films between wirings in semiconductor devices.
- As the insulating films for rewiring to be formed on semiconductor devices thin resin films having a thickness of 20 ⁇ m or smaller formed from a photosensitive polyimide resin or photosensitive polybenzoxazole resin are generally used.
- the thicknesses of inorganic films which can be formed by CVD are generally 1 ⁇ m or smaller when the productivity thereof is taken into account.
- the photosensitive polyimides see documents 1 to 4
- photosensitive polybenzoxazole see document 5
- actinic rays do not reach the interface between the substrate and the resin and, hence, it is difficult to form an image having a thickness of 20 ⁇ m or larger through the curing of the photosensitive materials.
- the negative photosensitive materials heretofore in use can form an image having a thickness of 20 ⁇ m or larger.
- use of the negative photosensitive materials has problems that only those parts near the surface to which actinic rays reach are crosslinked and cured and, hence, the resultant pattern has an umbrella shape called a reversed taper, and that because of the insufficient exposure amount, a semi-cured material remains as a residue after development.
- a photosensitive polyimide of the dissolution control type employing a 1,4-dihydropyridine derivative as a photosensitizer has recently been proposed (see documents 6 and 7).
- This photosensitive polyimide is free from the problem in existing negative materials that a residue of the photosensitive material remains after development.
- the disadvantage that the photosensitive polyimide gives a pattern having a taper shape can be mitigated to some degree by conducing a heating (post-exposure heating) treatment after exposure and before development.
- incorporation of polyethylene glycol as a development accelerator into the photosensitive polyimide has enabled the photosensitive material to give an image which has a sufficient heat treatment margin even when the thickness thereof after cure is as large as 20 ⁇ m or more (see documents 7 and 8).
- this photosensitive material tends to give patterns having a normal taper shape in contrast to negative materials heretofore in use, the resolution of such patterns comprising a thick film is about 40-50 ⁇ m at the most.
- photosensitive materials which have been proposed include a photosensitive epoxy resin.
- this epoxy resin has a higher permittivity and a higher dielectric loss than the photosensitive materials described above and these properties result in a reduced rather than increased signal voltage, leading to a decrease in SN ratio.
- An object of the invention is to provide a photosensitive resin composition which, when exposed to light through a photomask and then developed, can form a pattern comprising a polyimide film having a thickness of 20 ⁇ m or larger with high resolution.
- Another object of the invention is to provide a use of the composition, in particular, a method of forming a pattern comprising the polyimide film.
- the present invention provides a photosensitive resin composition which comprises
- the present invention further provides a method of forming a pattern comprising a polyimide film, which comprises forming a film of the photosensitive resin composition, exposing the film to light through a photomask, subjecting the film to post-exposure heating, developing the film, and then heating the developed film to imidize the poly(amic acid).
- a pattern comprising a polyimide film having a thickness of 20 ⁇ m or larger can be formed with high resolution.
- the poly(amic acid) is obtained by reacting a tetracarboxylic dianhydride with a diamine in a substantially equimolar proportion in an appropriate organic solvent such as, e.g., N,N-dimethylacetamide or N-metyl-2-pyrrolidone.
- an appropriate organic solvent such as, e.g., N,N-dimethylacetamide or N-metyl-2-pyrrolidone.
- tetracarboxylic dianhydride examples include 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,2-bis(2,3-dicarboxylphenyl)hexafluoropropane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA), bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)sulfone dianhydride, bis(
- examples of the diamine include 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylpropane, 3,3'-diaminodiphenylpropane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzen
- the photosensitive resin composition according to the present invention may be obtained by yielding a poly(amic acid) in an organic solvent in the manner described above and mixing an 1,4-dihydropyridine derivative and an imide acrylate compound with the poly(amic acid) solution to dissolve these ingredients.
- the 1,4-dihydropyridine derivative to be used in the present invention is represented by the general formula (I) : (wherein R 1 and R 2 each represent a hydrogen atom or an alkyl group having 1-4 carbon atoms; R 3 and R 4 each represent an alkyl or alkoxy group each having 1-4 carbon atoms; and R 5 represents a hydrogen atom, an alkyl group having 1-4 carbon atoms, or a carboxyalkyl group in which the alkyl moiety has 1-4 carbon atoms).
- Examples of this 1,4-dihydropyridine derivative hence include 1-ethyl-3,5-dimethoxycarbonyl-4-(2-nitrophenyl)-1,4-dihydropyridine, 1,2,6-trimethyl-3,5-dimethoxycarbonyl-4-(2-nitrophenyl)-1,4-dihydropyridine, 2,6-dimethyl-3,5-diacetyl-4-(2-nitrophenyl)-1,4-dihydropyridine, and 1-carboxyethyl-3,5-dimethoxycarbonyl-4-(2-nitrophenyl)-1,4-dihydropyridine.
- These 1,4-dihydropyridine derivatives may be used alone or in combination of two or more thereof.
- 1-ethyl-3,5-dimethoxycarbonyl-4-(2-nitrophenyl)-1,4-dihydropyridine is especially preferred of those 1,4-dihydropyridine derivatives.
- the 1,4-dihydropyridine derivative is used in an amount in the range of generally 5-25 parts by weight per 100 parts by weight of the sum of the tetracarboxylic dianhydride ingredient and the diamine ingredient.
- this photosensitive resin composition may give a polyimide film having reduced properties.
- the resultant photosensitive resin composition has reduced pattern-forming properties.
- the imide acrylate compound in the present invention is represented by general formula (II): (wherein R 1 represents a hydrogen atom or methyl and R represents a hydrocarbon group having 2 or more carbon atoms). R is preferably an alkylene group, most preferably ethylene. Examples of this imide acrylate compound hence include N-acryloyloxyethylhexahydrophthalimide.
- the imide acrylate compound is used in an amount in the range of generally 10-30 parts by weight per 100 parts by weight of the sum of the tetracarboxylic dianhydride and the diamine.
- the photosensitive resin composition of the invention can be obtained by yielding a poly(amic acid) in an organic solvent and mixing the 1,4-dihydropyridine derivative and the imide acrylate compound with the poly(amic acid) solution to dissolve these ingredients.
- This composition is applied to a wafer by, e.g., spin coating and dried to form a film. Subsequently, this film is exposed to light through a photomask and then heated at a temperature of generally 120-190°C for about 2-10 minutes (post-exposure heating).
- the exposed areas of the film formed from the photosensitive resin composition of the present invention come to have lower solubility in a developer than the unexposed areas.
- the film hence forms a negative latent image.
- This film, which has such a negative latent image is treated with an aqueous alkali solution to dissolve away the unexposed areas, i.e., to develop the film, whereby a negative image can be obtained.
- this negative image is heated to a high temperature in an inert gas atmosphere such as nitrogen or under vacuum to thereby cause the poly(amic acid) constituting the negative image to undergo cyclization and imidization and simultaneously pyrolyze and volatilize the 1,4-dihydropyridine derivative present as a photosensitizer in the negative image.
- an inert gas atmosphere such as nitrogen or under vacuum
- organic solvent examples include the aforementioned and other solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, and dimethyl sulfoxide.
- actinic rays such as ultraviolet or electron beams can be used.
- the wavelength of the exposure light is in the range of generally 300-450 nm, preferably 360-440 nm, and the integrated exposure amount is in the range of generally 100-1,000 mJ/cm 2 , preferably 200-700 mJ/cm 2 .
- aqueous alkali solution which is a developing solution
- an aqueous solution of an inorganic alkali such as sodium hydroxide or potassium hydroxide
- an aqueous solution of an organic alkali such as tetramethylammonium hydroxide. It is, however, desirable to use an aqueous solution of an organic alkali so as to avoid semiconductor fouling.
- a dissolution control agent such as, e.g., an alcohol may be added to the developing solution according to need.
- Usable development methods include the immersion method, spraying method, and paddle method. The development may be conducted at room temperature or with heating according to need.
- the heating temperature for polyimide formation is generally in the range of 250-450°C. In case where the heating temperature for polyimide formation is lower than 250°C, there is the possibility that part of the 1,4-dihydropyridine derivative might remain in the polyimide film to prevent the resultant polyimide film from having desirable properties. On the other hand, in case where the temperature exceeds 450°C, there is the possibility that the polyimide itself might deteriorate.
- the heating temperature for polyimide formation is preferably in the range of 300-400°C.
- the solution of a photosensitive resin composition was applied to a silicon wafer with a spin coater and dried on a 120°C hot plate for 10 minutes to obtain a coating film having a thickness of 54 ⁇ m.
- This coating film was exposed to ultraviolet through a photomask for 90 seconds using a 250-W ultrahigh-pressure mercury lamp and then heated on a 175°C hot plate for 10 minutes (post-exposure heating).
- the unexposed areas of the coating film were dissolved away by the spraying method (temperature, 45°C; pressure, 0.1 MPa) using a water/ethanol (1/1) solution of tetramethylammonium hydroxide (concentration, 5% by weight). Thereafter, the silicon wafer was rinsed with water to obtain a negative pattern.
- the pattern thus obtained was heated at 400°C for 2 hours in a nitrogen atmosphere to conduct imidization.
- a fine pattern comprising a polyimide film was obtained on the silicon wafer.
- Resolution was determined in terms of the resolution for an equally spaced L&S pattern and that for equally spaced square via holes. The results obtained are shown in Table 1.
- a photosensitive resin composition was obtained as a homogeneous solution in the same manner as in Example 1, except that 1-methyl-3,5-di(t-butoxycarbonyl)-4-(2-nitrophenyl)-1,4-dihydropyridine was used in place of the 1-ethyl-3,5-dimethoxycarbonyl-4-(2-nitrophenyl)-1,4-dihydropyridine.
- This solution was used to obtain a fine pattern comprising a polyimide film on a silicon wafer in the same manner as in Example 1. Resolution was determined in the same manner as in Example 1. The results obtained are shown in Table 1.
- a photosensitive resin composition was obtained as a homogeneous solution in the same manner as in Example 1, except that the poly(amic acid) solution prepared above was used. This composition was used to obtain a fine pattern comprising a polyimide film on a silicon wafer in the same manner as in Example 1. Resolution was determined in the same manner as in Example 1. The results obtained are shown in Table 1.
- Formation of a negative pattern comprising a polyimide film was attempted in the same manner as in Example 1, except that the photosensitive resin composition obtained above was used. However, the development after exposure of the coating film of the photosensitive resin composition failed to completely dissolve away the unexposed areas. This is because the photosensitive resin composition did not contain N-acryloyloxyethylhexahydrophthalimide.
- a photosensitive resin composition was obtained as a homogeneous solution in the same manner as in Example 1, except that polyethylene glycol having a weight-average molecular weight of 600 was used in place of the N-acryloyloxyethylhexahydrophthalimide.
- This composition was used to obtain a fine pattern comprising a polyimide film on a silicon wafer in the same manner as in Example 1. Resolution was determined in the same manner as in Example 1. The results obtained are shown in Table 1.
- Example Comparative Example 1 2 3 1 2 Coating film thickness (after drying) ( ⁇ m) 54 55 57 54 54 Coating film thickness after post-exposure heating ( ⁇ m) 38 38 40 36 38 Film thickness after development ( ⁇ m) 38 37 40 36 37 Film thickness after imidization ( ⁇ m) imidization ( ⁇ m) 28 27 30 26 27 Resolution (L&S) ( ⁇ m) 20 20 20 - 40 Resolution (square via holes) ( ⁇ m) 30 30 30 - 50
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- Materials For Photolithography (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Paints Or Removers (AREA)
Abstract
Description
- The present invention relates to a photosensitive resin composition capable of forming, with high resolution, a pattern comprising a polyimide film having a thickness of 20 µm or larger. The invention further relates to a use of the composition, in particular, a method of forming a pattern comprising the polyimide film.
- Thin inorganic films formed by CVD have usually been used as interlayer insulating films between wirings in semiconductor devices. As the insulating films for rewiring to be formed on semiconductor devices, thin resin films having a thickness of 20 µm or smaller formed from a photosensitive polyimide resin or photosensitive polybenzoxazole resin are generally used.
- In recent years, the operating frequencies of semiconductor devices are increasing so as to cope with the increases in the amount and rate of information communication. In addition, the trend toward size reduction in semiconductor devices for improving the portability and handiness of electronic appliances has resulted in an increased wiring density and a reduced wiring line width. As a result, a decrease in signal voltage due to wiring resistance has come to be pointed out, although this decrease has hitherto been not problematic. On the other hand, a device called a system-on-chip has been proposed. It is a semiconductor chip having all of functions which have hitherto been formed separately on respective semiconductor chips and connected to each other on a circuit board. In this technique, long wirings having a narrow line width are required because different functions are connected to each other on the same chip. It has been proposed to increase the thickness of these wirings on a semiconductor in order to prevent the decrease in signal voltage caused by wiring resistance. In this case, however, a wiring thickness of 10 µm or larger and an insulating layer thickness of 20 µm or larger are expected to be required in the future because the interlayer insulating film should have a thickness sufficiently larger than the wiring thickness.
- However, the thicknesses of inorganic films which can be formed by CVD are generally 1 µm or smaller when the productivity thereof is taken into account. Even in the case of the photosensitive polyimides (see documents 1 to 4) and photosensitive polybenzoxazole (see document 5) for use as passivation films in semiconductor devices, it is extremely difficult to deposit a film in a thickness of 20 µm or larger because of a decrease in resolution. Namely, in the case of positive photosensitive materials among those, actinic rays do not reach the interface between the substrate and the resin and, hence, it is difficult to form an image having a thickness of 20 µm or larger through the curing of the photosensitive materials. On the other hand, the negative photosensitive materials heretofore in use can form an image having a thickness of 20 µm or larger. However, use of the negative photosensitive materials has problems that only those parts near the surface to which actinic rays reach are crosslinked and cured and, hence, the resultant pattern has an umbrella shape called a reversed taper, and that because of the insufficient exposure amount, a semi-cured material remains as a residue after development.
- Under these circumstances, a photosensitive polyimide of the dissolution control type employing a 1,4-dihydropyridine derivative as a photosensitizer has recently been proposed (see documents 6 and 7). This photosensitive polyimide is free from the problem in existing negative materials that a residue of the photosensitive material remains after development. Furthermore, the disadvantage that the photosensitive polyimide gives a pattern having a taper shape can be mitigated to some degree by conducing a heating (post-exposure heating) treatment after exposure and before development. In particular, incorporation of polyethylene glycol as a development accelerator into the photosensitive polyimide has enabled the photosensitive material to give an image which has a sufficient heat treatment margin even when the thickness thereof after cure is as large as 20 µm or more (see documents 7 and 8). However, since this photosensitive material tends to give patterns having a normal taper shape in contrast to negative materials heretofore in use, the resolution of such patterns comprising a thick film is about 40-50 µm at the most.
- Other photosensitive materials which have been proposed include a photosensitive epoxy resin. However, this epoxy resin has a higher permittivity and a higher dielectric loss than the photosensitive materials described above and these properties result in a reduced rather than increased signal voltage, leading to a decrease in SN ratio.
- Document 1: JP-A-49-011541
- Document 2: JP-A-50-140922
- Document 3: JP-A-54-145794
- Document 4: JP-A-56-038038
- Document 5: JP-A-07-281441
- Document 6: JP-A-06-075376
- Document 7: JP-A-07-271034
- Document 8: JP-A-2002-148804
-
- The present invention has been achieved in order to eliminate the above-described problems of photosensitive resin compositions. An object of the invention is to provide a photosensitive resin composition which, when exposed to light through a photomask and then developed, can form a pattern comprising a polyimide film having a thickness of 20 µm or larger with high resolution. Another object of the invention is to provide a use of the composition, in particular, a method of forming a pattern comprising the polyimide film.
- The present invention provides a photosensitive resin composition which comprises
- (a) a poly(amic acid) ,
- (b) a 1,4-dihydropyridine derivative represented by the general formula (I): (wherein R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1-4 carbon atoms; R3 and R4 each independently represent an alkyl or alkoxy group each having 1-4 carbon atoms; and R5 represents a hydrogen atom, an alkyl group having 1-4 carbon atoms, or a carboxyalkyl group in which the alkyl moiety has 1-4 carbon atoms), and
- (c) an imide acrylate compound represented by the general formula (II): (wherein R1 represents a hydrogen atom or methyl and R represents a hydrocarbon group having 2 or more carbon atoms).
-
- The present invention further provides a method of forming a pattern comprising a polyimide film, which comprises forming a film of the photosensitive resin composition, exposing the film to light through a photomask, subjecting the film to post-exposure heating, developing the film, and then heating the developed film to imidize the poly(amic acid).
- According to the photosensitive resin composition of the invention, a pattern comprising a polyimide film having a thickness of 20 µm or larger can be formed with high resolution.
- The poly(amic acid) is obtained by reacting a tetracarboxylic dianhydride with a diamine in a substantially equimolar proportion in an appropriate organic solvent such as, e.g., N,N-dimethylacetamide or N-metyl-2-pyrrolidone.
- Examples of the tetracarboxylic dianhydride include 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,2-bis(2,3-dicarboxylphenyl)hexafluoropropane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA), bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)sulfone dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, pyromellitic dianhydride, and ethylene glycol bistrimellitate dianhydride. These may be used alone or in combination of two or more thereof.
- On the other hand, examples of the diamine include 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylpropane, 3,3'-diaminodiphenylpropane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)-2,2-dimethylpropane, hexamethylenediamine, 1,8-diaminooctane, 1,12-diaminododecane, 4,4'-diaminobenzophenone, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane. These also may be used alone or in combination of two or more thereof.
- The photosensitive resin composition according to the present invention may be obtained by yielding a poly(amic acid) in an organic solvent in the manner described above and mixing an 1,4-dihydropyridine derivative and an imide acrylate compound with the poly(amic acid) solution to dissolve these ingredients.
- The 1,4-dihydropyridine derivative to be used in the present invention is represented by the general formula (I) : (wherein R1 and R2 each represent a hydrogen atom or an alkyl group having 1-4 carbon atoms; R3 and R4 each represent an alkyl or alkoxy group each having 1-4 carbon atoms; and R5 represents a hydrogen atom, an alkyl group having 1-4 carbon atoms, or a carboxyalkyl group in which the alkyl moiety has 1-4 carbon atoms).
- Examples of this 1,4-dihydropyridine derivative hence include 1-ethyl-3,5-dimethoxycarbonyl-4-(2-nitrophenyl)-1,4-dihydropyridine, 1,2,6-trimethyl-3,5-dimethoxycarbonyl-4-(2-nitrophenyl)-1,4-dihydropyridine, 2,6-dimethyl-3,5-diacetyl-4-(2-nitrophenyl)-1,4-dihydropyridine, and 1-carboxyethyl-3,5-dimethoxycarbonyl-4-(2-nitrophenyl)-1,4-dihydropyridine. These 1,4-dihydropyridine derivatives may be used alone or in combination of two or more thereof. In the present invention, 1-ethyl-3,5-dimethoxycarbonyl-4-(2-nitrophenyl)-1,4-dihydropyridine is especially preferred of those 1,4-dihydropyridine derivatives.
- In the photosensitive resin composition of the present invention, the 1,4-dihydropyridine derivative is used in an amount in the range of generally 5-25 parts by weight per 100 parts by weight of the sum of the tetracarboxylic dianhydride ingredient and the diamine ingredient. In case where the amount of the 1,4-dihydropyridine derivative in the photosensitive resin composition is larger than 25 parts by weight per 100 parts by weight of the sum of the tetracarboxylic dianhydride and the diamine, this photosensitive resin composition may give a polyimide film having reduced properties. In case where the amount thereof is smaller than 5 parts by weight, the resultant photosensitive resin composition has reduced pattern-forming properties.
- The imide acrylate compound in the present invention is represented by general formula (II): (wherein R1 represents a hydrogen atom or methyl and R represents a hydrocarbon group having 2 or more carbon atoms). R is preferably an alkylene group, most preferably ethylene. Examples of this imide acrylate compound hence include N-acryloyloxyethylhexahydrophthalimide.
- In the photosensitive resin composition of the present invention, the imide acrylate compound is used in an amount in the range of generally 10-30 parts by weight per 100 parts by weight of the sum of the tetracarboxylic dianhydride and the diamine.
- The method of forming a pattern comprising a polyimide from the photosensitive resin composition of the invention is explained next. As stated above, the photosensitive resin composition of the invention can be obtained by yielding a poly(amic acid) in an organic solvent and mixing the 1,4-dihydropyridine derivative and the imide acrylate compound with the poly(amic acid) solution to dissolve these ingredients. This composition is applied to a wafer by, e.g., spin coating and dried to form a film. Subsequently, this film is exposed to light through a photomask and then heated at a temperature of generally 120-190°C for about 2-10 minutes (post-exposure heating).
- As a result of the exposure and the post-exposing heating, the exposed areas of the film formed from the photosensitive resin composition of the present invention come to have lower solubility in a developer than the unexposed areas. The film hence forms a negative latent image. This film, which has such a negative latent image, is treated with an aqueous alkali solution to dissolve away the unexposed areas, i.e., to develop the film, whereby a negative image can be obtained. Thereafter, this negative image is heated to a high temperature in an inert gas atmosphere such as nitrogen or under vacuum to thereby cause the poly(amic acid) constituting the negative image to undergo cyclization and imidization and simultaneously pyrolyze and volatilize the 1,4-dihydropyridine derivative present as a photosensitizer in the negative image. Thus, a pattern comprising a polyimide film can be obtained.
- Examples of the organic solvent include the aforementioned and other solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, and dimethyl sulfoxide.
- For exposing the film formed from the photosensitive resin composition of the present invention, actinic rays such as ultraviolet or electron beams can be used. When the film formed from the photosensitive resin composition is exposed to ultraviolet, the wavelength of the exposure light is in the range of generally 300-450 nm, preferably 360-440 nm, and the integrated exposure amount is in the range of generally 100-1,000 mJ/cm2, preferably 200-700 mJ/cm2.
- As the aqueous alkali solution, which is a developing solution, can be used, for example, an aqueous solution of an inorganic alkali such as sodium hydroxide or potassium hydroxide or an aqueous solution of an organic alkali such as tetramethylammonium hydroxide. It is, however, desirable to use an aqueous solution of an organic alkali so as to avoid semiconductor fouling. A dissolution control agent such as, e.g., an alcohol may be added to the developing solution according to need. Usable development methods include the immersion method, spraying method, and paddle method. The development may be conducted at room temperature or with heating according to need.
- The heating temperature for polyimide formation is generally in the range of 250-450°C. In case where the heating temperature for polyimide formation is lower than 250°C, there is the possibility that part of the 1,4-dihydropyridine derivative might remain in the polyimide film to prevent the resultant polyimide film from having desirable properties. On the other hand, in case where the temperature exceeds 450°C, there is the possibility that the polyimide itself might deteriorate. The heating temperature for polyimide formation is preferably in the range of 300-400°C.
- The present invention will be explained below by reference to Examples, but the invention should not be construed as being limited by these Examples in any way.
- In N,N-dimethylacetamide, 5.88 g of p-phenylenediamine, 2.04 g of 4,4'-diaminodiphenyl ether, and 0.84 g of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane were reacted with 20.0 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride at room temperature to obtain a solution of a poly(amic acid). In this poly(amic acid) solution were dissolved 2.88 g of 1-ethyl-3,5-dimethoxycarbonyl-4-(2-nitrophenyl)-1,4-dihydropyridine and 5.76 g of N-acryloyloxyethylhexahydrophthalimide. Thus, a photosensitive resin composition was obtained as a homogeneous solution.
- Subsequently, the solution of a photosensitive resin composition was applied to a silicon wafer with a spin coater and dried on a 120°C hot plate for 10 minutes to obtain a coating film having a thickness of 54 µm. This coating film was exposed to ultraviolet through a photomask for 90 seconds using a 250-W ultrahigh-pressure mercury lamp and then heated on a 175°C hot plate for 10 minutes (post-exposure heating). Subsequently, the unexposed areas of the coating film were dissolved away by the spraying method (temperature, 45°C; pressure, 0.1 MPa) using a water/ethanol (1/1) solution of tetramethylammonium hydroxide (concentration, 5% by weight). Thereafter, the silicon wafer was rinsed with water to obtain a negative pattern.
- The pattern thus obtained was heated at 400°C for 2 hours in a nitrogen atmosphere to conduct imidization. Thus, a fine pattern comprising a polyimide film was obtained on the silicon wafer. Resolution was determined in terms of the resolution for an equally spaced L&S pattern and that for equally spaced square via holes. The results obtained are shown in Table 1.
- A photosensitive resin composition was obtained as a homogeneous solution in the same manner as in Example 1, except that 1-methyl-3,5-di(t-butoxycarbonyl)-4-(2-nitrophenyl)-1,4-dihydropyridine was used in place of the 1-ethyl-3,5-dimethoxycarbonyl-4-(2-nitrophenyl)-1,4-dihydropyridine. This solution was used to obtain a fine pattern comprising a polyimide film on a silicon wafer in the same manner as in Example 1. Resolution was determined in the same manner as in Example 1. The results obtained are shown in Table 1.
- In N,N-dimethylacetamide, 6.3 g of p-phenylenediamine and 0.76 g of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane were reacted with 10.8 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride and 10.9 g of 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride to obtain a solution of a poly(amic acid).
- A photosensitive resin composition was obtained as a homogeneous solution in the same manner as in Example 1, except that the poly(amic acid) solution prepared above was used. This composition was used to obtain a fine pattern comprising a polyimide film on a silicon wafer in the same manner as in Example 1. Resolution was determined in the same manner as in Example 1. The results obtained are shown in Table 1.
- In N,N-dimethylacetamide, 5.88 g of p-phenylenediamine, 2.04 g of 4,4'-diaminodiphenyl ether, and 0.84 g of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane were reacted with 20.0 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride at room temperature to obtain a solution of a poly(amic acid). In this solution was dissolved 2.88 g of 1-ethyl-3,5-dimethoxycarbonyl-4-(2-nitrophenyl)-1,4-dihydropyridine. Thus, a photosensitive resin composition was obtained as a homogeneous solution.
- Formation of a negative pattern comprising a polyimide film was attempted in the same manner as in Example 1, except that the photosensitive resin composition obtained above was used. However, the development after exposure of the coating film of the photosensitive resin composition failed to completely dissolve away the unexposed areas. This is because the photosensitive resin composition did not contain N-acryloyloxyethylhexahydrophthalimide.
- A photosensitive resin composition was obtained as a homogeneous solution in the same manner as in Example 1, except that polyethylene glycol having a weight-average molecular weight of 600 was used in place of the N-acryloyloxyethylhexahydrophthalimide. This composition was used to obtain a fine pattern comprising a polyimide film on a silicon wafer in the same manner as in Example 1. Resolution was determined in the same manner as in Example 1. The results obtained are shown in Table 1.
Example Comparative Example 1 2 3 1 2 Coating film thickness (after drying) (µm) 54 55 57 54 54 Coating film thickness after post-exposure heating (µm) 38 38 40 36 38 Film thickness after development (µm) 38 37 40 36 37 Film thickness after imidization (µm) imidization (µm) 28 27 30 26 27 Resolution (L&S) (µm) 20 20 20 - 40 Resolution (square via holes) (µm) 30 30 30 - 50 - While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the scope thereof.
- This application is based on Japanese patent application No. 2004-076146 filed March 17, 2004, the entire contents thereof being hereby incorporated by reference.
Claims (3)
- A photosensitive resin composition which comprises:(a) a poly(amic acid) ,(b) a 1,4-dihydropyridine derivative represented by the general formula (I): wherein R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1-4 carbon atoms; R3 and R4 each independently represent an alkyl or alkoxy group each having 1-4 carbon atoms; and R5 represents a hydrogen atom, an alkyl group having 1-4 carbon atoms, or a carboxyalkyl group in which the alkyl moiety has 1-4 carbon atoms, and
- A method of forming a pattern comprising a polyimide film, which comprises forming a film of the photosensitive resin composition of claim 1, exposing the film to light through a photomask, subjecting the film to post-exposure heating, developing the film, and then heating the developed film to imidize the poly(amic acid).
- The method of forming a pattern comprising a polyimide film of claim 2, wherein the polyimide film has a thickness of 20 µm or larger.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004076146A JP4256806B2 (en) | 2004-03-17 | 2004-03-17 | Photosensitive resin composition and use thereof |
JP2004076146 | 2004-03-17 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP1577708A2 true EP1577708A2 (en) | 2005-09-21 |
EP1577708A3 EP1577708A3 (en) | 2009-05-13 |
EP1577708B1 EP1577708B1 (en) | 2010-04-14 |
Family
ID=34836540
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP05005613A Not-in-force EP1577708B1 (en) | 2004-03-17 | 2005-03-15 | Photosensitive resin composition and use of the same |
Country Status (6)
Country | Link |
---|---|
US (1) | US7008752B2 (en) |
EP (1) | EP1577708B1 (en) |
JP (1) | JP4256806B2 (en) |
CN (1) | CN100498529C (en) |
AT (1) | ATE464588T1 (en) |
DE (1) | DE602005020543D1 (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010181817A (en) * | 2009-02-09 | 2010-08-19 | Asahi Kasei E-Materials Corp | Photosensitive resin composition |
JP5644068B2 (en) * | 2009-07-06 | 2014-12-24 | 日立化成デュポンマイクロシステムズ株式会社 | Photosensitive resin composition, method for producing resist pattern, and hard disk suspension |
JP5208085B2 (en) * | 2009-10-14 | 2013-06-12 | 日東電工株式会社 | Photosensitive resin composition, method for producing circuit board with metal support using the same, and circuit board with metal support |
JP2011253044A (en) * | 2010-06-02 | 2011-12-15 | Nippon Kayaku Co Ltd | Photosensitive resin composition, its use and method of utilizing the same |
JP2012063645A (en) | 2010-09-17 | 2012-03-29 | Nitto Denko Corp | Photosensitive resin composition and circuit board with metal support using the composition |
SG11201606071WA (en) | 2014-01-24 | 2016-09-29 | Toray Industries | Negative photosensitive resin composition, cured film obtained by curing same, method for producing cured film, optical device provided with cured film, and backside-illuminated cmos image sensor |
JP7492880B2 (en) | 2020-08-03 | 2024-05-30 | 日東電工株式会社 | Polyimide precursor composition |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000267276A (en) * | 1999-03-18 | 2000-09-29 | Nitto Denko Corp | Transfer sheet |
WO2003038526A1 (en) * | 2001-10-30 | 2003-05-08 | Kaneka Corporation | Photosensitive resin composition and photosensitive films and laminates made by using the same |
JP2003186192A (en) * | 2001-12-19 | 2003-07-03 | Nitto Denko Corp | Photosensitive resin composition and polyimide resin |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4911541A (en) | 1972-06-01 | 1974-02-01 | ||
JPS5246723B2 (en) | 1974-04-26 | 1977-11-28 | ||
JPS5952822B2 (en) | 1978-04-14 | 1984-12-21 | 東レ株式会社 | Heat-resistant photosensitive material |
JPS606368B2 (en) | 1979-08-01 | 1985-02-18 | 東レ株式会社 | Photosensitive polyimide precursor |
JP3093055B2 (en) | 1992-07-07 | 2000-10-03 | 日東電工株式会社 | Heat resistant negative photoresist composition, photosensitive substrate, and negative pattern forming method |
JP3709997B2 (en) | 1994-03-29 | 2005-10-26 | 日東電工株式会社 | Heat resistant negative photoresist composition, photosensitive substrate, and negative pattern forming method |
JP3176795B2 (en) | 1994-04-06 | 2001-06-18 | 住友ベークライト株式会社 | Positive photosensitive resin composition |
JP2002148804A (en) | 2000-11-08 | 2002-05-22 | Nitto Denko Corp | Photosensitive resin composition and circuit board |
-
2004
- 2004-03-17 JP JP2004076146A patent/JP4256806B2/en not_active Expired - Lifetime
-
2005
- 2005-03-15 EP EP05005613A patent/EP1577708B1/en not_active Not-in-force
- 2005-03-15 DE DE602005020543T patent/DE602005020543D1/en active Active
- 2005-03-15 AT AT05005613T patent/ATE464588T1/en not_active IP Right Cessation
- 2005-03-17 US US11/081,516 patent/US7008752B2/en active Active
- 2005-03-17 CN CNB200510055133XA patent/CN100498529C/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000267276A (en) * | 1999-03-18 | 2000-09-29 | Nitto Denko Corp | Transfer sheet |
WO2003038526A1 (en) * | 2001-10-30 | 2003-05-08 | Kaneka Corporation | Photosensitive resin composition and photosensitive films and laminates made by using the same |
JP2003186192A (en) * | 2001-12-19 | 2003-07-03 | Nitto Denko Corp | Photosensitive resin composition and polyimide resin |
Also Published As
Publication number | Publication date |
---|---|
CN100498529C (en) | 2009-06-10 |
JP4256806B2 (en) | 2009-04-22 |
US7008752B2 (en) | 2006-03-07 |
DE602005020543D1 (en) | 2010-05-27 |
ATE464588T1 (en) | 2010-04-15 |
CN1670626A (en) | 2005-09-21 |
EP1577708B1 (en) | 2010-04-14 |
EP1577708A3 (en) | 2009-05-13 |
US20050208421A1 (en) | 2005-09-22 |
JP2005266075A (en) | 2005-09-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR102214856B1 (en) | Polyimide precursor, photosensitive resin composition containing said polyimide precursor, and cured-pattern-film manufacturing method and semiconductor device using said photosensitive resin composition | |
EP1577708B1 (en) | Photosensitive resin composition and use of the same | |
JP6888660B2 (en) | Resin composition containing polyimide precursor, method for manufacturing cured film and electronic components | |
KR20180076327A (en) | Polyimide resin and positive photosensitive resin composition | |
KR101969197B1 (en) | Positive photosensitive resin composition | |
KR101056962B1 (en) | Polyimide-based polymer and copolymer mixture thereof, and positive type photoresist composition comprising the same | |
JP5367809B2 (en) | Photosensitive resin composition and cured film | |
US7371506B2 (en) | Positive photosensitive resin composition | |
EP1705204B1 (en) | Photosensitive resin and a method of preparing the same | |
JPH1184645A (en) | Photosensitive resin composition | |
JP2005242328A (en) | Positive photosensitive resin composition, semiconductor device and display component using the positive photosensitive resin composition, and method for producing semiconductor device and display component | |
TW202336117A (en) | Resin composition, cured article, laminate, method for producing cured article, method for producing laminate, method for producing semiconductor device, and semiconductor device | |
WO2020246565A1 (en) | Photosensitive polyimide resin composition | |
JP3363580B2 (en) | Method for producing photosensitive resin composition and relief pattern | |
JP4461613B2 (en) | Photosensitive resin composition and pattern production method | |
TWI830255B (en) | Photosensitive polyimide resin composition | |
TWI846881B (en) | Photosensitive polyimide resin composition | |
Jin et al. | A novel positive‐type photosensitive polyimide having excellent transparency based on soluble block copolyimide with hydroxyl group and diazonaphthoquintone | |
JPH05310933A (en) | Production of polyimide soluble in solvent | |
JP3029316B2 (en) | Photosensitive resin composition for forming polyimide film pattern and semiconductor device using the same | |
JP2005134742A (en) | Photoresist and method for forming image by using the same | |
JP2022162611A (en) | Negative photosensitive resin composition, resin composition film, cured film, and semiconductor device | |
JP2023069530A (en) | Negative photosensitive resin composition, dry film, cured product, and electronic component | |
JPH07219225A (en) | Photosensitive resin composition | |
JP2002372782A (en) | Photosensitive resin composition and semiconductor device having pattern of the same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU MC NL PL PT RO SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL BA HR LV MK YU |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU MC NL PL PT RO SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL BA HR LV MK YU |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: G03F 7/037 20060101AFI20050720BHEP Ipc: C08G 73/10 20060101ALI20090404BHEP Ipc: G03F 7/40 20060101ALN20090404BHEP |
|
17P | Request for examination filed |
Effective date: 20090716 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: C08G 73/10 20060101ALI20090910BHEP Ipc: G03F 7/40 20060101ALN20090910BHEP Ipc: G03F 7/037 20060101AFI20090910BHEP Ipc: G03F 7/031 20060101ALI20090910BHEP |
|
AKX | Designation fees paid |
Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU MC NL PL PT RO SE SI SK TR |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU MC NL PL PT RO SE SI SK TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REF | Corresponds to: |
Ref document number: 602005020543 Country of ref document: DE Date of ref document: 20100527 Kind code of ref document: P |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: VDEP Effective date: 20100414 |
|
LTIE | Lt: invalidation of european patent or patent extension |
Effective date: 20100414 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100414 Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100725 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100414 Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100414 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100414 Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100414 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100814 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100414 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100414 Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100421 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100715 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100816 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100414 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100414 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100414 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100414 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100414 Ref country code: BE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100414 |
|
26N | No opposition filed |
Effective date: 20110117 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100414 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110331 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110331 Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110315 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110331 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110315 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100414 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100714 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100414 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 12 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 13 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20170213 Year of fee payment: 13 Ref country code: DE Payment date: 20170307 Year of fee payment: 13 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20170315 Year of fee payment: 13 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 602005020543 Country of ref document: DE |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20180315 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20181002 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180315 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180331 |